EP3044269B1 - Plasticiser for sealants and adhesives - Google Patents

Plasticiser for sealants and adhesives Download PDF

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Publication number
EP3044269B1
EP3044269B1 EP14761842.5A EP14761842A EP3044269B1 EP 3044269 B1 EP3044269 B1 EP 3044269B1 EP 14761842 A EP14761842 A EP 14761842A EP 3044269 B1 EP3044269 B1 EP 3044269B1
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EP
European Patent Office
Prior art keywords
composition according
cut
plasticizer
hydrocarbon cut
hydrocarbon
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Application number
EP14761842.5A
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German (de)
French (fr)
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EP3044269A1 (en
Inventor
Franck Bardin
Thorsten Bauer
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TotalEnergies Onetech SAS
Original Assignee
Total Marketing Services SA
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Priority to PL14761842T priority Critical patent/PL3044269T3/en
Publication of EP3044269A1 publication Critical patent/EP3044269A1/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/01—Hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0016—Plasticisers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/101—Esters; Ether-esters of monocarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/06—Homopolymers or copolymers of vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/34—Filling pastes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J123/04—Homopolymers or copolymers of ethene
    • C09J123/08—Copolymers of ethene
    • C09J123/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C09J123/0853—Vinylacetate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J177/00—Adhesives based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K3/1006—Materials in mouldable or extrudable form for sealing or packing joints or covers characterised by the chemical nature of one of its constituents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/101—Esters; Ether-esters of monocarboxylic acids
    • C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols

Definitions

  • the invention relates to a composition of hydrocarbon fluids useful as a plasticizer in the formulation of sealants and adhesives.
  • the present invention relates to a plasticizer without phthalates, with a low level of volatile organic compounds (or VOCs) and further comprising a portion of compounds of renewable origin.
  • the present invention also relates to the use of said composition for the formulation of sealants and adhesives.
  • plasticizers are common in certain families of mastics such as hybrid mastics (based on modified silicone polymers), acrylic mastics, Polyurethane mastics, Plastisols (PVC paste) and certain adhesives.
  • a plasticizer is a molecule or an oligomer, in the solid state or in the more or less viscous liquid state, added to formulations of different types of materials to make them more flexible, more resistant, more resilient or easier to handle.
  • An ideal plasticizer is compatible with the polymer matrix to avoid migration phenomena, low volatility, difficult to extract by liquids which will be in contact with the plasticized material, efficient with respect to certain properties such as flexibility, impact resistance, cold, heat and having good electrical resistivity. It will not oxidize and will be non-toxic, odorless, colorless and inexpensive.
  • Phthalates are products very commonly used as a plasticizer. But increasingly strong regulatory pressure is restricting their jobs in many countries because of their dangerousness for humans. Alternatives to their use are therefore necessary and highly sought after today.
  • VOCs Volatil Organic Compounds in English or VOC
  • these compounds tend either immediately or over time to evaporate and / or degrade and to be a source of emissions that are often toxic to the environment and more. particularly for human and animal health.
  • These emissions surrounding everyday life are a major source of indoor pollution in homes, offices and administrations and in any enclosed space with limited ventilation.
  • These emissions can be major when the materials are laid, but there can also be a longer-term effect through residual volatility as a function of time or even linked to the gradual degradation of the coating or of the adhesive composition or of the mastic.
  • Hydrocarbon-based fluids of gas oil, kerosene or white spirit type can also be used as a secondary plasticizer in various formulations including polymers or resins. This is the case for sealants or PVC pastes.
  • One of the applicant's main objectives is therefore to provide a composition which can be used as a phthalate-free plasticizer, for the formulation of building materials and materials intended for the automotive sector, such as sealants or certain types of adhesives.
  • Another of the applicant's objectives is to obtain a composition which can be used as a plasticizer with non-VOC characteristics, for the formulation of construction materials, of materials based on resins or of materials used in the automotive sector such as sealants, or certain types. types of adhesives.
  • Another objective of the Applicant is to provide a composition which can be used as a plasticizer compatible with use for the formulation of mastics and adhesives.
  • Another objective of the applicant is to provide a composition which can be used as a plasticizer allowing the formulation of mastics and adhesives having satisfactory curing, in particular according to the DIN ISO 7619 standard (for mastics).
  • a plastisol composition comprising a plastisol base such as polyvinyl chloride, a first plasticizer and a second plasticizer, the second plasticizer comprising a C1-2 alkyl monoester of a fatty acid containing at least 12 carbon atoms.
  • biodiesel is the name of a mixture of fatty acid methyl esters produced from vegetable oils.
  • Another objective of the Applicant is to provide a composition which can be used as a plasticizer allowing the formulation of sealants and adhesives which do not exhibit bleeding.
  • Another objective of the Applicant is to provide a composition which can be used as a plasticizer allowing the formulation of sealants and adhesives exhibiting satisfactory drying, that is to say drying in less than 24 hours for a film with a thickness of 2 mm. .
  • Another objective of the Applicant is to provide a composition which can be used as a plasticizer allowing the formulation of sealants and adhesives having an adequate viscosity, that is to say a viscosity of between 2000 and 8000 Pa.s.
  • Another objective of the Applicant is to provide a composition which can be used as a plasticizer allowing the formulation of sealants and adhesives having a satisfactory skin formation time, that is to say a skin formation time at room temperature of between 5 and 45 minutes.
  • Another objective of the applicant is to provide a composition which can be used as a plasticizer allowing the formulation of sealants and adhesives having good shear strength according to standard DIN EN 14293 (for sealants).
  • Another objective of the Applicant is to provide a composition which can be used as a plasticizer allowing the formulation of mastics and adhesives having a modulus of elasticity according to standard DIN 53504 or according to the appropriate standard DIN 52455-1 (for mastics).
  • Another objective of the applicant is to provide a composition which can be used as a plasticizer allowing the formulation of mastics and adhesives having good tensile strength according to the DIN 53504 standard (for mastics).
  • Another objective of the Applicant is to provide a composition which can be used as a plasticizer allowing the formulation of mastics and adhesives exhibiting a satisfactory elongation at break according to standard DIN 53504 (for mastics).
  • Another objective of the applicant is to provide a composition which can be used as a plasticizer allowing the formulation of mastics and adhesives exhibiting satisfactory elastic recovery according to DIN EN ISO 7389 (for mastics).
  • the hydrocarbon cut is a hydrotreated, hydrocracked or catalytically cracked hydrocarbon cut.
  • the hydrocarbon cut is a dearomatized and optionally desulphurized hydrocarbon cut.
  • the hydrocarbon cut has a boiling point of between 230 and 400 ° C.
  • the hydrocarbon cut has a kinematic viscosity at 40 ° C. of between 2 and 22 mm 2 / s according to the ASTM D445 standard.
  • the hydrocarbon cut has a pour point ranging from -50 to + 10 ° C according to the ASTM D97 standard.
  • the hydrocarbon cut has an aromatic compound content measured by UV of less than 300 ppm, preferably less than 200 ppm and even more preferably less than 100 ppm.
  • the fatty acid monoester is a methyl ester of C14-18 fatty acids.
  • the mass ratio between the fatty acid monoester and the hydrocarbon cut or the cut resulting from the conversion of biomass is between 5:95 and 75:25, preferably between 10:90 and 60:40, more preferably between 20:80 and 45:55, even more preferably between 30:70 and 40:60.
  • said composition comprises from 10 to 50% by weight of said polymer, preferably from 20 to 30%.
  • said composition comprises from 10 to 30% by weight of plasticizer, preferably from 10 to 25%.
  • the invention relates to the use of the plasticizer as described above in sealants or adhesives.
  • the plasticizer according to the invention comprises at least one hydrocarbon cut or a cut resulting from the conversion of biomass.
  • the plasticizer according to the invention comprises at least one hydrocarbon cut.
  • hydrocarbon cut means a cut resulting from the distillation of crude oil, preferably resulting from atmospheric distillation and / or vacuum distillation of crude oil, preferably resulting from atmospheric distillation followed by vacuum distillation. .
  • the hydrocarbon cut according to the invention is also preferably subjected to hydrotreatment, hydrocracking or catalytic cracking stages.
  • the hydrocarbon cut according to the invention is also preferably subjected to stages of dearomatization and optionally desulfurization.
  • the hydrocarbon cut according to the invention can also preferably be subjected to a hydrodewaxing step.
  • the feed obtained after the distillation step (s) is a gas oil feed, this gas oil feed being subjected to the hydrotreatment, hydrocracking, catalytic cracking or hydrodewaxing steps, optionally followed by the dearomatization and optionally desulphurization steps.
  • the hydrocarbon cut can be a mixture of hydrocarbon cuts undergoing the steps described above.
  • the hydrocarbon cut as described above has a distillation range ID (in ° C) such as 230 ID 400 and more preferably such as 250 ID 380.
  • the hydrocarbon cut can comprise one or more fractions of distillation intervals included in that of said cut.
  • the hydrocarbon cut according to the invention generally comprises more than 60% by weight of paraffinic compounds, preferably more than 65%, even more preferably more than 70%.
  • the hydrocarbon cut according to the invention generally consists of a majority of isoparaffins and a minority of normal paraffins.
  • the hydrocarbon cut contains more than 50% by weight of isoparaffins and less than 20% by weight of normal paraffins.
  • the hydrocarbon cut according to the invention generally comprises less than 50% by weight of naphthenic compounds, preferably less than 40%, even more preferably less than 30%.
  • the hydrocarbon cut according to the invention is preferably free of aromatics.
  • free is meant, preferably, a hydrocarbon cut comprising less than 300 ppm of aromatics, preferably less than 200 ppm, even more preferably less than 100 ppm measured by UV spectrometry.
  • the hydrocarbon cut according to the invention has a sulfur content of less than 10 ppm and preferably less than 2 ppm.
  • the hydrocarbon cut according to the invention generally has a kinematic viscosity at 40 ° C of between 2 and 22 mm 2 / s, preferably between 2 and 15 mm 2 / s and more preferably between 3 and 13 mm 2 / s according to ASTM D445.
  • the hydrocarbon cut according to the invention has a pour point according to the ASTM D97 standard of between -50 and +10 ° C, preferably between -40 and 0 ° C, even more preferably between -30 and -10 ° vs.
  • the cut resulting from the conversion of biomass can be produced from raw biological materials selected from the group consisting of vegetable oils, animal fats, fish oils and mixtures thereof.
  • Suitable raw organic materials include the following: rapeseed oil, canola oil, rapeseed oil, tall oil, sunflower oil, soybean oil, hemp oil, olive oil, flaxseed oil, colza oil, mustard, palm oil, peanut oil, castor oil, coconut oil, animal fats such as bacon, tallow or pan, recycled edible fats, raw materials from genetic engineering and biological raw materials produced by microorganisms such as algae and bacteria. Condensation products, esters or other derivatives obtained from raw biological materials can also serve as raw materials.
  • a solvent of biological origin is then produced using, for example, a process which firstly comprises a hydrodeoxygenation (HDO) step to decompose the structure of the constituent biological esters or triglycerides and to eliminate the compounds containing oxygen, phosphorus and sulfur while at the same time producing the hydrogenation of olefinic bonds.
  • HDO hydrodeoxygenation
  • This is followed by isomerization of the product thus obtained leading to branching of the hydrocarbon chain and to an improvement in the properties of the paraffin at low temperatures. It is for example possible to fractionate the product to obtain the desired cuts.
  • the hydrocarbon cut according to the invention also has the advantage of being easily available on the market, of being relatively economical within the chain of products from petroleum distillation or from the conversion of biomass.
  • the plasticizer according to the invention also comprises at least one fatty acid monoester. It is understood that it can also be a mixture of several fatty acids, each of the fatty acids being mono-esterified.
  • the fatty acid esters are obtained by esterification of free fatty acids or by transesterification of animal and / or vegetable oils (or triglycerides of fatty acids) with an alcohol. During esterification or transesterification, small amounts of fatty acids may remain in the form of monoglyceride, diglyceride, triglyceride or fatty acids in free form.
  • the fatty acid monoester according to the invention can comprise negligible amounts of fatty acids in the form of monoglyceride, diglyceride, triglyceride or in free form.
  • the fatty acid monoester according to the invention is in the form of a monoester with more than 80% by mass, preferably between 90 and 100%, more preferably between 95 and 98%.
  • the amounts of fatty acids in the form of monoglyceride, diglyceride, triglyceride or in free form are negligible and do not represent more than 15% by mass of the monoester of fatty acids according to the invention, preferably not more than 10%, more preferably not more than 6%, still more preferably not more than 4%.
  • the fatty acid monoester according to the invention does not comprise more than 5% by mass of fatty acids in the form of monoglyceride, preferably not more than 1%.
  • the fatty acid monoester according to the invention does not comprise more than 5% by mass of fatty acids in the form of diglyceride, preferably not more than 2%.
  • the fatty acid monoester according to the invention does not comprise more than 5% by mass of fatty acids in the form of triglyceride, preferably not more than 1%.
  • the fatty acid monoester according to the invention does not comprise more than 6% by mass of fatty acids in free form, preferably not more than 3%.
  • the fatty acids of the fatty acid monoester according to the invention are fatty acids comprising from 6 to 24 carbon atoms, preferably from 14 to 22 carbon atoms, more preferably from 16 to 18 carbon atoms, fatty acids comprising 18 carbon atoms, being the majority fatty acids.
  • the fatty acid ester is not chosen from esters of glycerol and of tall oil fatty acid.
  • the fatty acid monoester according to the invention can be a C 1 -C 4 alkyl monoester, such as a methyl monoester, an ethyl monoester, an n -propyl monoester, an i -propyl monoester. , n- butyl monoester, s-butyl monoester, t-butyl monoester.
  • the monoester is a methyl monoester.
  • the preferred fatty acid monoester is a fatty acid methyl ester registered under the number CAS 67762-26-9 .
  • the plasticizer according to the invention comprises from 5 to 75% by weight of fatty acid monoester, more preferably from 10 to 60%, even more preferably from 20 to 45%, even more preferably from 30 to 40%.
  • the plasticizer comprises 20 to 60% by weight of fatty acid monoester.
  • the plasticizer comprises 45 to 75% of a hydrocarbon cut or of a cut resulting from the conversion of biomass.
  • the plasticizer composition comprises from 25% to 95% by weight of hydrocarbon cut or cut resulting from the conversion of biomass, more preferably from 40 to 90%, even more preferably from 55 to 80%, even more preferably from 60 to 70%.
  • the mass ratio between the fatty acid monoester and the hydrocarbon cut or the cut resulting from the conversion of biomass is between 5:95 and 75:25, preferably between 10:90 and 60:40, more preferably between 20:80 and 45:55, even more preferably between 30:70 and 40:60.
  • the plasticizer according to the invention is free from compounds of phthalate type.
  • free according to the invention is meant a plasticizer comprising less than 1% by mass of phthalates, relative to the mass of plasticizer, preferably less than 0.5%, more preferably less than 0.1%, even more preferably less than 0.01%.
  • the plasticizer according to the invention generally has a kinematic viscosity at 40 ° C. ranging from 5 to 22 mm 2 / s, preferably ranging from 5 to 15 mm 2 / s according to the ASTM D445 standard.
  • the invention also relates to a mastic composition
  • a mastic composition comprising at least one polymer chosen from the group consisting of a polyether comprising two terminal functions of silane type, a polyurethane comprising two terminal functions of silane type, or a mixture of these, the plasticizer composition as described above and at least one crosslinking agent.
  • the polymer is a polyether comprising two terminal functions of silane type.
  • the mastic composition comprises from 10 to 50% by weight of said polymer, preferably from 20 to 30%.
  • the mastic composition comprises from 10 to 30% by weight of said plasticizer composition, preferably from 10 to 25%.
  • the mastic composition also conventionally comprises at least one thickener, a filler, a crosslinking agent and / or a catalyst.
  • a subject of the invention is also an adhesive composition, preferably a thermoplastic adhesive composition, comprising at least one polyamide, an ethylene vinyl acetate copolymer, the plasticizer composition as described above and a tackifying resin.
  • the sealant and adhesive compositions according to the invention have the remarkable characteristic of containing less than 0.1% by weight of phthalates, relative to the weight of the composition, preferably less than 0.05%, more preferably less. 0.01%, even more preferably less than 0.001%.
  • thermoplastic sealants and adhesives compositions as described are phthalate-free and have low VOCs in order to meet the regulatory requirements in force.
  • plasticizing composition according to the invention in sealants and adhesives is described.
  • SMP sealants include the ST-PE (Silane terminated Polyether) and ST-PU (Silane terminated Poyurethane) product families.
  • Table 1 groups together the chemical characteristics of the ST-PE sealant used for the various evaluations. ⁇ u> Table 1 ⁇ /u> Formulation % mass Chemical Nature / Properties Polymer MS 203H 15 ST-PE / Polymer Polymer MS 303H 10 ST-PE / Polymer Plasticizer 17 See mixtures described in Table 2 below Crayvallac SLX 4.5 PA-wax / thickener Carbital 110S 51.1 Chalk / charge SLX activation; T> 70 ° C Cooling to T ⁇ 40 ° C Dynasilan VTMO 0.8 Vinyltrimethoxysilan / drying agent Drying of additives for 1 hour DynasilanAMMO 1.1 3-Aminopropylmethoxysilane / crosslinking agent Cooling to T ⁇ 30 ° C, Crosslinking for 30 min TIB Kat 223 0.3 Dioctyltindiethanolate / Catalyst CatalystTIB Kat 422 0.2 Dioctyltin- si
  • Table 2 groups together the results obtained for the various sealant formulations. ⁇ u> Table 2 ⁇ /u> Example Plasticizer Plasticizer constituents ratio Hardening (1) Penetrant (2) Surface aspect (3) 1 comparative 17% HYDROSEAL G3H - OK yes (3d) Dried 2 comparative 17% HYDROSEAL G340H - OK yes, strong after 1 day (1d) wet 3 comparative 17% DIDP - OK no dried 4 8.5% FAME / 8.5% HYDROSEAL G340H 50/50 OK no Dried 5 8% FAME / 9% HYDROSEAL G340H 47/53 OK no dried 6 5% FAME / 12% HYDROSEAL G3H 29/71 OK no dried 7 7% FAME / 10% HYDROSEAL G400H 41/59 OK no dried (1) The hardening of the sealant is evaluated to the touch 24 hours after its application, (2) To evaluate the bleeding, the application of the sealant is made on a Bristol sheet of the Exacompta 13308E type. After hardening
  • Table 3 groups together the results obtained for other sealant formulations with the reference phthalates as plasticizer (comparative example 1a) and a plasticizer according to the invention (example 8 according to the invention).
  • Example 1a contains 17% of a plasticizer which is Jayflex DIDP.
  • the formulation of Example 8 contains 17% of a plasticizer which is a mixture of Hydroseal G340H and fatty acid methyl esters (FAME).
  • the mass percentages of Hydroseal G340H and esters methyl fatty acids (FAME) are respectively 8% and 9% relative to the weight of the formulation.
  • the mechanical properties of the ST-PE mastic containing the composition EMAG / Hydroseal G340H as a plasticizer are as good or even better than those of a mastic containing DIDP as a plasticizer.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Sealing Material Composition (AREA)

Description

DOMAINE DE L'INVENTIONFIELD OF THE INVENTION

L'invention concerne une composition de fluides hydrocarbonés utilisable en tant que plastifiant dans la formulation de mastics et adhésifs.The invention relates to a composition of hydrocarbon fluids useful as a plasticizer in the formulation of sealants and adhesives.

La présente invention concerne un plastifiant sans phtalates, à bas taux de composés organiques volatiles (ou COV) et comprenant en outre une partie de composés d'origine renouvelable.The present invention relates to a plasticizer without phthalates, with a low level of volatile organic compounds (or VOCs) and further comprising a portion of compounds of renewable origin.

La présente invention concerne aussi l'utilisation de ladite composition pour la formulation de mastics et d'adhésifs.The present invention also relates to the use of said composition for the formulation of sealants and adhesives.

CONTEXTE TECHNIQUE DE L'INVENTIONTECHNICAL BACKGROUND OF THE INVENTION

De nombreux produits sont utilisés dans les matériaux de construction, par exemple pour les revêtements de sol, les mastics ou encore les joints de sanitaires. L'ajout de plastifiants est courant dans certaines familles de mastics tels que les mastics hybrides (à base de polymères siliconés modifiés), les mastics acryliques, les mastics Polyuréthanes, les Plastisols (pâte PVC) et certains adhésifs. Un plastifiant est une molécule ou un oligomère, à l'état solide ou à l'état liquide plus ou moins visqueux, ajouté aux formulations de différents types de matériaux pour les rendre plus flexibles, plus résistants, plus résilients ou plus faciles à manipuler.Many products are used in construction materials, for example for floor coverings, mastics or even sanitary joints. The addition of plasticizers is common in certain families of mastics such as hybrid mastics (based on modified silicone polymers), acrylic mastics, Polyurethane mastics, Plastisols (PVC paste) and certain adhesives. A plasticizer is a molecule or an oligomer, in the solid state or in the more or less viscous liquid state, added to formulations of different types of materials to make them more flexible, more resistant, more resilient or easier to handle.

Un plastifiant idéal est compatible avec la matrice polymère pour éviter les phénomènes de migration, peu volatil, difficilement extractible par les liquides qui seront en contact avec le matériau plastifié, performant vis-à-vis de certaines propriétés comme la souplesse, résistant aux chocs, au froid, à la chaleur et ayant une bonne résistivité électrique. Il ne s'oxydera pas et sera non toxique, inodore, incolore et peu coûteux.An ideal plasticizer is compatible with the polymer matrix to avoid migration phenomena, low volatility, difficult to extract by liquids which will be in contact with the plasticized material, efficient with respect to certain properties such as flexibility, impact resistance, cold, heat and having good electrical resistivity. It will not oxidize and will be non-toxic, odorless, colorless and inexpensive.

Les phtalates sont des produits très couramment utilisés comme plastifiant. Mais la pression réglementaire de plus en plus forte restreint leurs emplois dans de nombreux pays du fait de leur dangerosité pour l'homme. Des alternatives à leur utilisation sont donc aujourd'hui nécessaires et très recherchées.Phthalates are products very commonly used as a plasticizer. But increasingly strong regulatory pressure is restricting their jobs in many countries because of their dangerousness for humans. Alternatives to their use are therefore necessary and highly sought after today.

D'autre part, les contraintes réglementaires récentes apportées par les limitations en Composés Organiques Volatiles ou COV (Volatil Organic Compounds en anglais ou VOC) dans les matériaux de construction sont également à prendre en compte. En effet, ces composés ont tendance soit tout de suite, soit avec le temps à s'évaporer et/ou se dégrader et à être une source d'émissions souvent toxiques pour l'environnement et plus particulièrement pour les santés humaine et animale. Ces émissions environnant la vie de tous les jours constituent une source importante de pollution intérieure des habitations, des bureaux et des administrations et de tout espace enfermé dont l'aération est limitée. Ces émissions peuvent être majeures au moment de la pose des matériaux mais il peut également y avoir un effet à plus long terme par volatilité rémanente en fonction du temps ou même liée à la dégradation progressive du revêtement ou de la composition adhésive ou du mastic.On the other hand, the recent regulatory constraints brought by the limitations of Volatile Organic Compounds or VOCs (Volatil Organic Compounds in English or VOC) in construction materials must also be taken into account. Indeed, these compounds tend either immediately or over time to evaporate and / or degrade and to be a source of emissions that are often toxic to the environment and more. particularly for human and animal health. These emissions surrounding everyday life are a major source of indoor pollution in homes, offices and administrations and in any enclosed space with limited ventilation. These emissions can be major when the materials are laid, but there can also be a longer-term effect through residual volatility as a function of time or even linked to the gradual degradation of the coating or of the adhesive composition or of the mastic.

Les fluides hydrocarbonés de type gazole, kérosène ou white spirit peuvent également être utilisés comme plastifiant secondaire dans différentes formulations incluant des polymères ou résines. C'est le cas pour les mastics ou les pâtes PVC.Hydrocarbon-based fluids of gas oil, kerosene or white spirit type can also be used as a secondary plasticizer in various formulations including polymers or resins. This is the case for sealants or PVC pastes.

Mais leur utilisation est aujourd'hui limitée par leur moindre compatibilité dans le polymère par rapport aux phtalates. Des phénomènes de migration en surface, de ressuage, des défauts d'aspect de surface constatés empêchent la production de formules sans phtalates contenant uniquement des fluides hydrocarbonés.But their use is limited today by their lower compatibility in the polymer with respect to phthalates. Surface migration phenomena, bleeding, surface appearance defects observed prevent the production of phthalate-free formulas containing only hydrocarbon fluids.

De part les contraintes réglementaires de plus en plus importantes, une solution technique est requise pour permettre le remplacement des phtalates dans des formulations stables et économiquement avantageuses de matériaux de construction à bas taux de COV. <insérer page 2a>Due to increasingly important regulatory constraints, a technical solution is required to allow the replacement of phthalates in stable and economically advantageous formulations of low VOC building materials. <insert page 2a>

Un des principaux objectifs de la demanderesse est donc de proposer une composition utilisable comme plastifiant exempte de phtalates, pour la formulation de matériaux de constructions et de matériaux destinés au secteur automobile tels que les mastics, ou certains types d'adhésifs.One of the applicant's main objectives is therefore to provide a composition which can be used as a phthalate-free plasticizer, for the formulation of building materials and materials intended for the automotive sector, such as sealants or certain types of adhesives.

Un autre des objectifs de la demanderesse est d'obtenir une composition utilisable comme plastifiant à caractères non COV, pour la formulation de matériaux de construction, de matériaux à base de résines ou de matériaux utilisés dans le secteur automobile tels que les mastics, ou certains types d'adhésifs.Another of the applicant's objectives is to obtain a composition which can be used as a plasticizer with non-VOC characteristics, for the formulation of construction materials, of materials based on resins or of materials used in the automotive sector such as sealants, or certain types. types of adhesives.

Un autre objectif de la demanderesse est de proposer une composition utilisable comme plastifiant compatible avec une utilisation pour la formulation de mastics et d'adhésifs.Another objective of the Applicant is to provide a composition which can be used as a plasticizer compatible with use for the formulation of mastics and adhesives.

Un autre objectif de la demanderesse est de proposer une composition utilisable comme plastifiant permettant la formulation de mastics et adhésifs ayant un durcissement satisfaisant, notamment selon la norme DIN ISO 7619 (pour les mastics).Another objective of the applicant is to provide a composition which can be used as a plasticizer allowing the formulation of mastics and adhesives having satisfactory curing, in particular according to the DIN ISO 7619 standard (for mastics).

Le document US 2001/044486 décrit une composition de plastisols comprenant une base plastisol telle que du polychlorure de vinyle, un premier plastifiant et un second plastifiant, le second plastifiant comprenant un monoester alkyl en C1-2 d'un acide gras contenant au moins 12 atomes de carbone.The document US 2001/044486 describes a plastisol composition comprising a plastisol base such as polyvinyl chloride, a first plasticizer and a second plasticizer, the second plasticizer comprising a C1-2 alkyl monoester of a fatty acid containing at least 12 carbon atoms.

Le document WO 2007/006489 décrit l'utilisation de biodiesel comme plastifiant de compositions de polymères. Ces polymères peuvent être des polyéthers modifiés par du silane ou des polyuréthanes modifiés par du silane. Le biodiesel est l'appellation d'un mélange d'esters méthyliques d'acides gras produit à partir d'huiles végétales.The document WO 2007/006489 describes the use of biodiesel as a plasticizer of polymer compositions. These polymers can be polyethers modified with silane or polyurethanes modified with silane. Biodiesel is the name of a mixture of fatty acid methyl esters produced from vegetable oils.

Un autre objectif de la demanderesse est de proposer une composition utilisable comme plastifiant permettant la formulation de mastics et adhésifs ne présentant pas de ressuage.Another objective of the Applicant is to provide a composition which can be used as a plasticizer allowing the formulation of sealants and adhesives which do not exhibit bleeding.

Un autre objectif de la demanderesse est de proposer une composition utilisable comme plastifiant permettant la formulation de mastics et adhésifs présentant un séchage satisfaisant, c'est-à-dire un séchage en moins de 24 heures pour un film d'une épaisseur de 2 mm.Another objective of the Applicant is to provide a composition which can be used as a plasticizer allowing the formulation of sealants and adhesives exhibiting satisfactory drying, that is to say drying in less than 24 hours for a film with a thickness of 2 mm. .

Un autre objectif de la demanderesse est de proposer une composition utilisable comme plastifiant permettant la formulation de mastics et adhésifs présentant une viscosité adéquate, c'est-à-dire une viscosité comprise entre 2000 et 8000 Pa.s.Another objective of the Applicant is to provide a composition which can be used as a plasticizer allowing the formulation of sealants and adhesives having an adequate viscosity, that is to say a viscosity of between 2000 and 8000 Pa.s.

Un autre objectif de la demanderesse est de proposer une composition utilisable comme plastifiant permettant la formulation de mastics et adhésifs présentant un temps de formation de peau satisfaisant, c'est-à-dire un temps de formation de peau à température ambiante compris entre 5 et 45 minutes.Another objective of the Applicant is to provide a composition which can be used as a plasticizer allowing the formulation of sealants and adhesives having a satisfactory skin formation time, that is to say a skin formation time at room temperature of between 5 and 45 minutes.

Un autre objectif de la demanderesse est de proposer une composition utilisable comme plastifiant permettant la formulation de mastics et adhésifs présentant une bonne résistance au cisaillement selon la norme DIN EN 14293 (pour les mastics).Another objective of the applicant is to provide a composition which can be used as a plasticizer allowing the formulation of sealants and adhesives having good shear strength according to standard DIN EN 14293 (for sealants).

Un autre objectif de la demanderesse est de proposer une composition utilisable comme plastifiant permettant la formulation de mastics et adhésifs présentant un module d'élasticité selon la norme DIN 53504 ou selon la norme DIN 52455-1 adéquate (pour les mastics).Another objective of the Applicant is to provide a composition which can be used as a plasticizer allowing the formulation of mastics and adhesives having a modulus of elasticity according to standard DIN 53504 or according to the appropriate standard DIN 52455-1 (for mastics).

Un autre objectif de la demanderesse est de proposer une composition utilisable comme plastifiant permettant la formulation de mastics et adhésifs présentant une bonne résistance à la traction selon la norme DIN 53504 (pour les mastics).Another objective of the applicant is to provide a composition which can be used as a plasticizer allowing the formulation of mastics and adhesives having good tensile strength according to the DIN 53504 standard (for mastics).

Un autre objectif de la demanderesse est de proposer une composition utilisable comme plastifiant permettant la formulation de mastics et adhésifs présentant un allongement à la rupture satisfaisant selon la norme DIN 53504 (pour les mastics).Another objective of the Applicant is to provide a composition which can be used as a plasticizer allowing the formulation of mastics and adhesives exhibiting a satisfactory elongation at break according to standard DIN 53504 (for mastics).

Un autre objectif de la demanderesse est de proposer une composition utilisable comme plastifiant permettant la formulation de mastics et adhésifs présentant une reprise élastique satisfaisante selon la norme DIN EN ISO 7389 (pour les mastics).Another objective of the applicant is to provide a composition which can be used as a plasticizer allowing the formulation of mastics and adhesives exhibiting satisfactory elastic recovery according to DIN EN ISO 7389 (for mastics).

RESUME DE L'INVENTIONSUMMARY OF THE INVENTION

L'invention concerne une composition comprenant :

  1. a) au moins un polymère choisi dans le groupe consistant en un polyéther comportant deux fonctions terminales de type silane, un polyuréthane comportant deux fonctions terminales de type silane, un polyamide, ou un melange de ceux-ci ;
  2. b) un plastifiant pour mastics et adhésifs, ledit plastifiant comprenant :
    1. i) au moins une coupe hydrocarbonée ou une coupe issue de la conversion de la biomasse, ladite coupe pouvant être produite à partir de matériaux biologiques bruts sélectionnés dans le groupe consistant en des huiles végétales, des graisses animales, des huiles de poisson et des mélanges de celles-ci, les matériaux biologiques bruts subissant une étape d'hydrodésoxygénation (HDO) pour décomposer la structure des esters ou triglycérides biologiques constitutifs et pour éliminer les composés contenant de l'oxygène, du phosphore et du soufre tout en produisant en même temps l'hydrogénation des liaisons oléfiniques, suivi par une isomérisation du produit ainsi obtenu conduisant à la ramification de la chaîne hydrocarbure ; et
    2. ii) au moins un monoester d'acides gras, les acides gras du monoester d'acides gras comprenant de 6 à 24 atomes de carbone ;
    3. iii) moins de 1% en poids de phtalates
  3. c) au moins un composé choisi dans le groupe consistant en un épaississant, une charge, un agent de réticulation, un catalyseur de réticulation et une résine tackifiante, ou un mélange de ceux-ci.
The invention relates to a composition comprising:
  1. a) at least one polymer chosen from the group consisting of a polyether comprising two terminal functions of silane type, a polyurethane comprising two terminal functions of silane type, a polyamide, or a mixture thereof;
  2. b) a plasticizer for sealants and adhesives, said plasticizer comprising:
    1. i) at least one hydrocarbon cut or one cut resulting from the conversion of biomass, said cut being able to be produced from raw biological materials selected from the group consisting of vegetable oils, animal fats, fish oils and mixtures of these, the raw biological materials undergoing a hydrodeoxygenation (HDO) step to break down the structure of the constituent biological esters or triglycerides and to remove compounds containing oxygen, phosphorus and sulfur while at the same time producing hydrogenation of the olefinic bonds, followed by isomerization of the product thus obtained leading to branching of the hydrocarbon chain; and
    2. ii) at least one fatty acid monoester, the fatty acids of the fatty acid monoester comprising from 6 to 24 carbon atoms;
    3. iii) less than 1% by weight of phthalates
  3. c) at least one compound selected from the group consisting of a thickener, a filler, a crosslinking agent, a crosslinking catalyst and a tackifying resin, or a mixture thereof.

De préférence, le plastifiant pour mastics et adhésifs comprend :

  1. a) au moins une coupe hydrocarbonée et
  2. b) au moins un monoester d'acides gras.
Preferably, the plasticizer for sealants and adhesives comprises:
  1. a) at least one hydrocarbon cut and
  2. b) at least one fatty acid monoester.

De préférence, la coupe hydrocarbonée est une coupe hydrocarbonée hydrotraitée, hydrocraquée ou craquée catalytiquement.Preferably, the hydrocarbon cut is a hydrotreated, hydrocracked or catalytically cracked hydrocarbon cut.

De préférence, la coupe hydrocarbonée est une coupe hydrocarbonée désaromatisée et éventuellement désulfuréePreferably, the hydrocarbon cut is a dearomatized and optionally desulphurized hydrocarbon cut.

De préférence, la coupe hydrocarbonée présente une température d'ébullition comprise entre 230 et 400 °C.Preferably, the hydrocarbon cut has a boiling point of between 230 and 400 ° C.

De préférence, la coupe hydrocarbonée présente une viscosité cinématique à 40°C comprise entre 2 et 22 mm2/s selon la norme ASTM D445.Preferably, the hydrocarbon cut has a kinematic viscosity at 40 ° C. of between 2 and 22 mm 2 / s according to the ASTM D445 standard.

De préférence, la coupe hydrocarbonée présente un point d'écoulement allant de -50 à + 10 °C selon la norme ASTM D97.Preferably, the hydrocarbon cut has a pour point ranging from -50 to + 10 ° C according to the ASTM D97 standard.

De préférence, la coupe hydrocarbonée présente une teneur en composés aromatiques mesurée par UV inférieure à 300 ppm, de préférence inférieure à 200 ppm et encore plus préférentiellement inférieure à 100 ppm.Preferably, the hydrocarbon cut has an aromatic compound content measured by UV of less than 300 ppm, preferably less than 200 ppm and even more preferably less than 100 ppm.

De préférence, le monoester d'acide gras est un ester méthylique d'acides gras en C14-18.Preferably, the fatty acid monoester is a methyl ester of C14-18 fatty acids.

De préférence, le rapport massique entre le monoester d'acide gras et la coupe hydrocarbonée ou la coupe issue de la conversion de la biomasse est compris entre 5:95 et 75:25, de préférence entre 10:90 et 60:40, plus préférentiellement entre 20:80 et 45:55, encore plus préférentiellement entre 30:70 et 40:60.Preferably, the mass ratio between the fatty acid monoester and the hydrocarbon cut or the cut resulting from the conversion of biomass is between 5:95 and 75:25, preferably between 10:90 and 60:40, more preferably between 20:80 and 45:55, even more preferably between 30:70 and 40:60.

Selon un mode de réalisation, ladite composition comprend de 10 à 50 % en poids dudit polymère, de préférence de 20 à 30 %.According to one embodiment, said composition comprises from 10 to 50% by weight of said polymer, preferably from 20 to 30%.

Selon un mode de réalisation, ladite composition comprend de 10 à 30 % en poids de plastifiant, de préférence de 10 à 25 %.According to one embodiment, said composition comprises from 10 to 30% by weight of plasticizer, preferably from 10 to 25%.

Selon un mode de réalisation, la composition est une composition de mastic comprenant:

  • au moins un polymère choisi dans le groupe consistant en un polyéther comportant deux fonctions terminales de type silane, un polyuréthane comportant deux fonctions terminales de type silane, ou un mélange de ceux-ci ;
  • le plastifiant tel que décrit ci-dessus ;
  • et au moins un agent réticulant.
According to one embodiment, the composition is a mastic composition comprising:
  • at least one polymer chosen from the group consisting of a polyether comprising two terminal functions of silane type, a polyurethane comprising two terminal functions of silane type, or a mixture of these;
  • the plasticizer as described above;
  • and at least one crosslinking agent.

Selon un mode de réalisation, la composition est une composition d'adhésif comprenant:

  • au moins un polyamide,
  • un copolymère éthylène-acétate de vinyle,
  • le plastifiant tel que décrit ci-dessus,
  • une résine tackifiante.
According to one embodiment, the composition is an adhesive composition comprising:
  • at least one polyamide,
  • an ethylene-vinyl acetate copolymer,
  • the plasticizer as described above,
  • a tackifying resin.

L'invention concerne enfin l'utilisation du plastifiant tel que décrit ci-dessus dans des mastics ou adhésifs.Finally, the invention relates to the use of the plasticizer as described above in sealants or adhesives.

DESCRIPTION DETAILLEE DE L'INVENTIONDETAILED DESCRIPTION OF THE INVENTION

Le plastifiant selon l'invention comprend au moins une coupe hydrocarbonée ou une coupe issue de la conversion de la biomasse.The plasticizer according to the invention comprises at least one hydrocarbon cut or a cut resulting from the conversion of biomass.

De préférence, le plastifiant selon l'invention comprend au moins une coupe hydrocarbonée.Preferably, the plasticizer according to the invention comprises at least one hydrocarbon cut.

On entend par coupe hydrocarbonée selon l'invention, une coupe issue de la distillation du pétrole brut, de préférence issue de la distillation atmosphérique et/ou distillation sous vide du pétrole brut, de préférence issue de la distillation atmosphérique suivie de la distillation sous vide.The term “hydrocarbon cut” according to the invention means a cut resulting from the distillation of crude oil, preferably resulting from atmospheric distillation and / or vacuum distillation of crude oil, preferably resulting from atmospheric distillation followed by vacuum distillation. .

La coupe hydrocarbonée selon l'invention est aussi de préférence soumise à des étapes d'hydrotraitement, hydrocraquage ou craquage catalytique.The hydrocarbon cut according to the invention is also preferably subjected to hydrotreatment, hydrocracking or catalytic cracking stages.

La coupe hydrocarbonée selon l'invention est aussi de préférence soumise à des étapes de désaromatisation et éventuellement désulfuration.The hydrocarbon cut according to the invention is also preferably subjected to stages of dearomatization and optionally desulfurization.

La coupe hydrocarbonée selon l'invention peut aussi de préférence être soumise à une étape d'hydrodéparaffinage.The hydrocarbon cut according to the invention can also preferably be subjected to a hydrodewaxing step.

De préférence, la charge obtenue après la ou les étapes de distillation est une charge gazole, cette charge gazole étant soumise aux étapes d'hydrotraitement, hydrocraquage, craquage catalytique ou hydrodéparaffinage, suivi éventuellement des étapes de désaromatisation et éventuellement de désulfuration.Preferably, the feed obtained after the distillation step (s) is a gas oil feed, this gas oil feed being subjected to the hydrotreatment, hydrocracking, catalytic cracking or hydrodewaxing steps, optionally followed by the dearomatization and optionally desulphurization steps.

La coupe hydrocarbonée peut être un mélange de coupes hydrocarbonées subissant les étapes décrites ci-dessus.The hydrocarbon cut can be a mixture of hydrocarbon cuts undergoing the steps described above.

La coupe hydrocarbonée telle que décrite ci-dessus, présente un intervalle de distillation ID (en °C) tel que 230≤ ID ≤ 400 et plus préférentiellement tel que 250 ≤ ID ≤ 380. La coupe hydrocarbonée peut comprendre une ou plusieurs fractions d'intervalles de distillation compris dans celui de ladite coupe.The hydrocarbon cut as described above has a distillation range ID (in ° C) such as 230 ID 400 and more preferably such as 250 ID 380. The hydrocarbon cut can comprise one or more fractions of distillation intervals included in that of said cut.

La coupe hydrocarbonée selon l'invention comprend généralement plus de 60% en poids de composés paraffiniques, de préférence plus de 65%, encore plus préférentiellement plus de 70%.The hydrocarbon cut according to the invention generally comprises more than 60% by weight of paraffinic compounds, preferably more than 65%, even more preferably more than 70%.

La coupe hydrocarbonée selon l'invention est généralement constituée d'une majorité d'isoparaffines et d'une minorité de normales paraffines. De préférence la coupe hydrocarbonée contient plus de 50% en poids d'isoparaffines et moins de 20% en poids de normales paraffines.The hydrocarbon cut according to the invention generally consists of a majority of isoparaffins and a minority of normal paraffins. Preferably, the hydrocarbon cut contains more than 50% by weight of isoparaffins and less than 20% by weight of normal paraffins.

La coupe hydrocarbonée selon l'invention comprend généralement moins de 50% en poids de composés naphténiques, de préférence moins de 40%, encore plus préférentiellement moins de 30%.The hydrocarbon cut according to the invention generally comprises less than 50% by weight of naphthenic compounds, preferably less than 40%, even more preferably less than 30%.

La coupe hydrocarbonée selon l'invention est de préférence exempte d'aromatiques. Par exempt, on entend, de préférence, une coupe hydrocarbonée comprenant moins de 300 ppm d'aromatiques, de préférence moins de 200 ppm, encore plus préférentiellement moins de 100 ppm mesurées par spectrométrie UV.The hydrocarbon cut according to the invention is preferably free of aromatics. By free is meant, preferably, a hydrocarbon cut comprising less than 300 ppm of aromatics, preferably less than 200 ppm, even more preferably less than 100 ppm measured by UV spectrometry.

De préférence, la coupe hydrocarbonée selon l'invention, a une teneur en soufre inférieure à 10 ppm et préférentiellement inférieure à 2 ppm.Preferably, the hydrocarbon cut according to the invention has a sulfur content of less than 10 ppm and preferably less than 2 ppm.

La coupe hydrocarbonée selon l'invention a généralement une viscosité cinématique à 40°C comprise entre 2 et 22 mm2/s, de préférence entre 2 et 15 mm2/s et de manière plus préférentielle entre 3 et 13 mm2/s selon la norme ASTM D445.The hydrocarbon cut according to the invention generally has a kinematic viscosity at 40 ° C of between 2 and 22 mm 2 / s, preferably between 2 and 15 mm 2 / s and more preferably between 3 and 13 mm 2 / s according to ASTM D445.

La coupe hydrocarbonée selon l'invention a un point d'écoulement selon la norme ASTM D97 compris entre -50 et +10 °C, de préférence compris entre -40 et 0 °C, encore plus préférentiellement compris entre -30 et -10°C.The hydrocarbon cut according to the invention has a pour point according to the ASTM D97 standard of between -50 and +10 ° C, preferably between -40 and 0 ° C, even more preferably between -30 and -10 ° vs.

La coupe issue de la conversion de la biomasse peut être produite à partir de matériaux biologiques bruts sélectionnés dans le groupe consistant en des huiles végétales, des graisses animales, des huiles de poisson et des mélanges de celles-ci. Les matériaux biologiques bruts appropriés comprennent les suivants : huile de graines de colza, huile de canola, huile de colza, huile de tall, huile de tournesol, huile de soja, huile de chanvre, huile d'olive, huile de lin, huile de moutarde, huile de palme, huile d'arachide, huile de ricin, huile de coco, graisses animales comme le lard, le suif ou la panne, graisses alimentaires recyclées, matières premières issues du génie génétique et matières premières biologiques produites par des microorganismes comme des algues et bactéries. Des produits de condensation, esters ou autres dérivés obtenus à partir de matériaux biologiques bruts peuvent également servir de matières premières.The cut resulting from the conversion of biomass can be produced from raw biological materials selected from the group consisting of vegetable oils, animal fats, fish oils and mixtures thereof. Suitable raw organic materials include the following: rapeseed oil, canola oil, rapeseed oil, tall oil, sunflower oil, soybean oil, hemp oil, olive oil, flaxseed oil, colza oil, mustard, palm oil, peanut oil, castor oil, coconut oil, animal fats such as bacon, tallow or pan, recycled edible fats, raw materials from genetic engineering and biological raw materials produced by microorganisms such as algae and bacteria. Condensation products, esters or other derivatives obtained from raw biological materials can also serve as raw materials.

Un solvant d'origine biologique est alors produit en utilisant par exemple un procédé qui comprend tout d'abord une étape d'hydrodésoxygénation (HDO) pour décomposer la structure des esters ou triglycérides biologiques constitutifs et pour éliminer les composés contenant de l'oxygène, du phosphore et du soufre tout en produisant en même temps l'hydrogénation des liaisons oléfiniques. Ceci est suivi par une isomérisation du produit ainsi obtenu conduisant à la ramification de la chaîne hydrocarbure et à une amélioration des propriétés de la paraffine à basses températures. Il est par exemple possible de fractionner le produit pour obtenir les coupes désirées.A solvent of biological origin is then produced using, for example, a process which firstly comprises a hydrodeoxygenation (HDO) step to decompose the structure of the constituent biological esters or triglycerides and to eliminate the compounds containing oxygen, phosphorus and sulfur while at the same time producing the hydrogenation of olefinic bonds. This is followed by isomerization of the product thus obtained leading to branching of the hydrocarbon chain and to an improvement in the properties of the paraffin at low temperatures. It is for example possible to fractionate the product to obtain the desired cuts.

La coupe hydrocarbonée selon l'invention a par ailleurs l'avantage d'être facilement disponible sur le marché, d'être relativement économique au sein de la chaîne des produits de la distillation pétrolière ou de la conversion de la biomasse.The hydrocarbon cut according to the invention also has the advantage of being easily available on the market, of being relatively economical within the chain of products from petroleum distillation or from the conversion of biomass.

Le plastifiant selon l'invention comprend également au moins un monoester d'acides gras. Il est entendu qu'il peut s'agir également d'un mélange de plusieurs acides gras, chacun des acides gras étant mono-estérifié.The plasticizer according to the invention also comprises at least one fatty acid monoester. It is understood that it can also be a mixture of several fatty acids, each of the fatty acids being mono-esterified.

Les esters d'acides gras sont obtenus par estérification des acides gras libres ou par transestérification des huiles animales et/ou végétales (ou triglycérides d'acides gras) avec un alcool. Lors de l'estérification ou de la transestérification, il peut subsister des petites quantités d'acides gras sous forme de monoglycéride, diglycéride, triglycéride ou d'acides gras sous forme libre.The fatty acid esters are obtained by esterification of free fatty acids or by transesterification of animal and / or vegetable oils (or triglycerides of fatty acids) with an alcohol. During esterification or transesterification, small amounts of fatty acids may remain in the form of monoglyceride, diglyceride, triglyceride or fatty acids in free form.

Ainsi, même si le monoester d'acides gras selon l'invention est très majoritairement sous forme de monoester, il peut comprendre des quantités négligeables d'acides gras sous forme de monoglycéride, diglycéride, triglycéride ou sous forme libre.Thus, even if the fatty acid monoester according to the invention is very predominantly in the form of a monoester, it can comprise negligible amounts of fatty acids in the form of monoglyceride, diglyceride, triglyceride or in free form.

Le monoester d'acides gras selon l'invention est sous forme de monoester à plus de 80% en masse, de préférence entre 90 et 100%, plus préférentiellement entre 95 et 98%. Les quantités d'acides gras sous forme de monoglycéride, diglycéride, triglycéride ou sous forme libre sont négligeables et ne représentent pas plus de 15% en masse du monoester d'acides gras selon l'invention, de préférence pas plus de 10%, plus préférentiellement pas plus de 6%, encore plus préférentiellement pas plus de 4%.The fatty acid monoester according to the invention is in the form of a monoester with more than 80% by mass, preferably between 90 and 100%, more preferably between 95 and 98%. The amounts of fatty acids in the form of monoglyceride, diglyceride, triglyceride or in free form are negligible and do not represent more than 15% by mass of the monoester of fatty acids according to the invention, preferably not more than 10%, more preferably not more than 6%, still more preferably not more than 4%.

En particulier, le monoester d'acides gras selon l'invention ne comprend pas plus de 5% en masse d'acides gras sous forme de monoglycéride, de préférence pas plus de 1%. En particulier, le monoester d'acides gras selon l'invention ne comprend pas plus de 5% en masse d'acides gras sous forme de diglycéride, de préférence pas plus de 2%. En particulier, le monoester d'acides gras selon l'invention ne comprend pas plus de 5% en masse d'acides gras sous forme de triglycéride, de préférence pas plus de 1%. En particulier, le monoester d'acides gras selon l'invention ne comprend pas plus de 6% en masse d'acides gras sous forme libre, de préférence pas plus de 3%.In particular, the fatty acid monoester according to the invention does not comprise more than 5% by mass of fatty acids in the form of monoglyceride, preferably not more than 1%. In particular, the fatty acid monoester according to the invention does not comprise more than 5% by mass of fatty acids in the form of diglyceride, preferably not more than 2%. In particular, the fatty acid monoester according to the invention does not comprise more than 5% by mass of fatty acids in the form of triglyceride, preferably not more than 1%. In particular, the fatty acid monoester according to the invention does not comprise more than 6% by mass of fatty acids in free form, preferably not more than 3%.

Les acides gras du monoester d'acides gras selon l'invention, sont des acides gras comprenant de 6 à 24 atomes de carbone, de préférence de 14 à 22 atomes de carbone, plus préférentiellement de 16 à 18 atomes de carbone, les acides gras comprenant 18 atomes de carbone, étant les acides gras majoritaires.The fatty acids of the fatty acid monoester according to the invention are fatty acids comprising from 6 to 24 carbon atoms, preferably from 14 to 22 carbon atoms, more preferably from 16 to 18 carbon atoms, fatty acids comprising 18 carbon atoms, being the majority fatty acids.

Selon un mode de réalisation, l'ester d'acide gras n'est pas choisi parmi les esters de glycérol et d'acide gras de tallöl.According to one embodiment, the fatty acid ester is not chosen from esters of glycerol and of tall oil fatty acid.

Le monoester d'acide gras selon l'invention peut être un monoester d'alkyle en C1-C4, tels que un monoester de méthyle, un monoester d'éthyle, un monoester de n-propyle, un monoester de i-propyle, un monoester de n-butyle, un monoester de s-butyle, un monoester de t-butyle. De préférence, le monoester est un monoester de méthyle.The fatty acid monoester according to the invention can be a C 1 -C 4 alkyl monoester, such as a methyl monoester, an ethyl monoester, an n -propyl monoester, an i -propyl monoester. , n- butyl monoester, s-butyl monoester, t-butyl monoester. Preferably, the monoester is a methyl monoester.

Le monoester d'acides gras préféré est un ester méthylique d'acide gras enregistré sous le numéro CAS 67762-26-9 .The preferred fatty acid monoester is a fatty acid methyl ester registered under the number CAS 67762-26-9 .

De préférence, le plastifiant selon l'invention comprend de 5 à 75 % en poids de monoester d'acides gras, plus préférentiellement de 10 à 60%, encore plus préférentiellement de 20 à 45%, encore plus préférentiellement de 30 à 40%.Preferably, the plasticizer according to the invention comprises from 5 to 75% by weight of fatty acid monoester, more preferably from 10 to 60%, even more preferably from 20 to 45%, even more preferably from 30 to 40%.

Selon un mode de réalisation, le plastifiant comprend de 20 à 60 % en poids de monoester d'acides gras.According to one embodiment, the plasticizer comprises 20 to 60% by weight of fatty acid monoester.

Selon un mode de réalisation, le plastifiant comprend de 45 à 75% d'une coupe hydrocarbonée ou d'une coupe issue de la conversion de la biomasse.According to one embodiment, the plasticizer comprises 45 to 75% of a hydrocarbon cut or of a cut resulting from the conversion of biomass.

De préférence, la composition de plastifiant comprend de 25 % à 95% en poids de coupe hydrocarbonée ou de coupe issue de la conversion de la biomasse, plus préférentiellement de 40 à 90%, encore plus préférentiellement de 55 à 80%, encore plus préférentiellement de 60 à 70%.Preferably, the plasticizer composition comprises from 25% to 95% by weight of hydrocarbon cut or cut resulting from the conversion of biomass, more preferably from 40 to 90%, even more preferably from 55 to 80%, even more preferably from 60 to 70%.

De préférence, le rapport massique entre le monoester d'acide gras et la coupe hydrocarbonée ou la coupe issue de la conversion de la biomasse est compris entre 5:95 et 75:25, de préférence entre 10:90 et 60:40, plus préférentiellement entre 20:80 et 45:55, encore plus préférentiellement entre 30:70 et 40:60.Preferably, the mass ratio between the fatty acid monoester and the hydrocarbon cut or the cut resulting from the conversion of biomass is between 5:95 and 75:25, preferably between 10:90 and 60:40, more preferably between 20:80 and 45:55, even more preferably between 30:70 and 40:60.

Le plastifiant selon l'invention est exempt de composés de type phtalate. Par exempt selon l'invention, on entend un plastifiant comprenant moins de 1% en masse de phtalates, par rapport à la masse de plastifiant, de préférence moins de 0,5%, plus préférentiellement moins de 0,1%, encore plus préférentiellement moins de 0,01%.The plasticizer according to the invention is free from compounds of phthalate type. By free according to the invention is meant a plasticizer comprising less than 1% by mass of phthalates, relative to the mass of plasticizer, preferably less than 0.5%, more preferably less than 0.1%, even more preferably less than 0.01%.

Le plastifiant selon l'invention a généralement une viscosité cinématique à 40°C allant de 5 à 22 mm2/s, de préférence allant de 5 à 15 mm2/s selon la norme ASTM D445.The plasticizer according to the invention generally has a kinematic viscosity at 40 ° C. ranging from 5 to 22 mm 2 / s, preferably ranging from 5 to 15 mm 2 / s according to the ASTM D445 standard.

L'invention concerne également une composition de mastic comprenant au moins un polymère choisi dans le groupe consistant en un polyéther comportant deux fonctions terminales de type silane, un polyuréthane comportant deux fonctions terminales de type silane, ou un mélange de ceux-ci, la composition de plastifiant telle que décrite ci-dessus et au moins un agent réticulant.The invention also relates to a mastic composition comprising at least one polymer chosen from the group consisting of a polyether comprising two terminal functions of silane type, a polyurethane comprising two terminal functions of silane type, or a mixture of these, the plasticizer composition as described above and at least one crosslinking agent.

De préférence, le polymère est un polyéther comportant deux fonctions terminales de type silane.Preferably, the polymer is a polyether comprising two terminal functions of silane type.

Avantageusement la composition de mastic comprend de 10 à 50 % en poids dudit polymère, de préférence de 20 à 30 %.Advantageously, the mastic composition comprises from 10 to 50% by weight of said polymer, preferably from 20 to 30%.

Avantageusement la composition de mastic comprend de 10 à 30 % en poids de ladite composition de plastifiant, de préférence de 10 à 25 %.Advantageously, the mastic composition comprises from 10 to 30% by weight of said plasticizer composition, preferably from 10 to 25%.

De manière à satisfaire aux exigences mécaniques et physico-chimiques la composition de mastic comprend également de manière classique au moins un épaississant, une charge, un agent de réticulation et/ou un catalyseur.In order to meet the mechanical and physicochemical requirements, the mastic composition also conventionally comprises at least one thickener, a filler, a crosslinking agent and / or a catalyst.

L'invention a aussi pour objet une composition d'adhésif, de préférence une composition d'adhésif thermoplastique, comprenant au moins un polyamide, un copolymère d'éthylène acétate de vinyle, la composition de plastifiant selon telle que décrite ci-dessus et une résine tackifiante.A subject of the invention is also an adhesive composition, preferably a thermoplastic adhesive composition, comprising at least one polyamide, an ethylene vinyl acetate copolymer, the plasticizer composition as described above and a tackifying resin.

Les compositions de mastics et d'adhésifs selon l'invention ont la caractéristique remarquable de contenir moins de 0,1% en poids de phtalates, par rapport à la masse de la composition, de préférence moins de 0,05%, plus préférentiellement moins de 0,01%, encore plus préférentiellement moins de 0,001%.The sealant and adhesive compositions according to the invention have the remarkable characteristic of containing less than 0.1% by weight of phthalates, relative to the weight of the composition, preferably less than 0.05%, more preferably less. 0.01%, even more preferably less than 0.001%.

Les compositions de mastics et d'adhésifs thermoplastique telles que décrites sont sans phtalates et à bas taux de COV afin de satisfaire aux exigences réglementaires en vigueur.The thermoplastic sealants and adhesives compositions as described are phthalate-free and have low VOCs in order to meet the regulatory requirements in force.

Il est décrit l'utilisation de la composition plastifiante selon l'invention dans des mastics et des adhésifs.The use of the plasticizing composition according to the invention in sealants and adhesives is described.

EXEMPLESEXAMPLES

Dans la suite de la présente description, des exemples sont donnés à titre illustratif de la présente invention et ne visent en aucun cas à en limiter la portée.In the remainder of the present description, examples are given by way of illustration of the present invention and are in no way intended to limit its scope.

Différentes formulations de mastic hybride à base de polymères siliconés modifiés (en anglais Silyl Modified Polymer ou SMP) ont été évaluées. Ces mastics SMP incluent les familles de produits ST-PE (Silane terminated Polyether) et ST-PU (Silane terminated Poyurethane).Different formulations of hybrid mastic based on modified silicone polymers (in English Silyl Modified Polymer or SMP) have been evaluated. These SMP sealants include the ST-PE (Silane terminated Polyether) and ST-PU (Silane terminated Poyurethane) product families.

Les exemples suivants décrivent les compositions de mastics SMP comprenant les différents plastifiants ci-dessous:

  • une coupe hydrocarbonée hydrocraquée telle que l'HYDROSEAL G3H ou l'HYDROSEAL G400H commercialisées par la société TOTAL FLUIDES, exemple comparatif 1,
  • une coupe hydrocarbonée hydrodéparaffinée telle que l'HYDROSEAL G340H commercialisée par la société TOTAL FLUIDES, exemple comparatif 2,
  • du di-isodécyl phthalate (ou DIDP) comme référence pour les phtalates, exemple comparatif 3,
  • un mélange d'esters méthyliques d'acides gras ou EMAG (en anglais FAME ou fatty acid methyl ester) + HYDROSEAL G3H ou HYDROSEAL G340H ou HYDROSEAL G400H, exemples selon l'invention 4, 5, 6 et 7 dans différentes proportions.
The following examples describe the SMP sealant compositions comprising the various plasticizers below:
  • a hydrocracked hydrocarbon cut such as HYDROSEAL G3H or HYDROSEAL G400H sold by the company TOTAL FLUIDES, comparative example 1,
  • a hydrodewaxed hydrocarbon cut such as HYDROSEAL G340H sold by the company TOTAL FLUIDES, comparative example 2,
  • di-isodecyl phthalate (or DIDP) as a reference for phthalates, comparative example 3,
  • a mixture of fatty acid methyl esters or FAME (in English FAME or fatty acid methyl ester) + HYDROSEAL G3H or HYDROSEAL G340H or HYDROSEAL G400H, examples according to the invention 4, 5, 6 and 7 in different proportions.

Le tableau 1 regroupe les caractéristiques chimiques du mastic ST-PE utilisé pour les différentes évaluations. Tableau 1 Formulation % masse Nature Chimique / Propriétés Polymère MS 203H 15 ST-PE / Polymère Polymère MS 303H 10 ST-PE / Polymère Plastifiant 17 Cf. mélanges décrits au tableau 2 ci-dessous Crayvallac SLX 4,5 PA-wax / épaississant Carbital 110S 51,1 Chalk / charge Activation SLX ; T>70°C Refroidissement à T<40°C Dynasilan VTMO 0,8 Vinyltrimethoxysilan/ agent séchant Séchage des additifs pendant 1heure DynasilanAMMO 1,1 3-Aminopropylmethoxysilane / agent de réticulation Refroidissement à T<30°C, Réticulation pendant 30 min TIB Kat 223 0,3 Dioctyltindiethanolate/Catalyseur CatalystTIB Kat 422 0,2 Dioctyltin- silane -blend / Catalyseur Table 1 groups together the chemical characteristics of the ST-PE sealant used for the various evaluations. <u> Table 1 </u> Formulation % mass Chemical Nature / Properties Polymer MS 203H 15 ST-PE / Polymer Polymer MS 303H 10 ST-PE / Polymer Plasticizer 17 See mixtures described in Table 2 below Crayvallac SLX 4.5 PA-wax / thickener Carbital 110S 51.1 Chalk / charge SLX activation; T> 70 ° C Cooling to T <40 ° C Dynasilan VTMO 0.8 Vinyltrimethoxysilan / drying agent Drying of additives for 1 hour DynasilanAMMO 1.1 3-Aminopropylmethoxysilane / crosslinking agent Cooling to T <30 ° C, Crosslinking for 30 min TIB Kat 223 0.3 Dioctyltindiethanolate / Catalyst CatalystTIB Kat 422 0.2 Dioctyltin- silane -blend / Catalyst

Le tableau 2 regroupe les résultats obtenus pour les différentes formulations de mastics. Tableau 2 Exemple Plastifiant Rapport constituants du plastifiant Durcissement(1) Ressuage (2) Aspect Surface (3) 1 comparatif 17% HYDROSEAL G3H - ok oui (3j) Sèche 2 comparatif 17% HYDROSEAL G340H - ok oui, fort après 1 jour (1j) mouillée 3 comparatif 17% DIDP - ok non sèche 4 8,5% EMAG / 8,5% HYDROSEAL G340H 50/50 ok non Sèche 5 8% EMAG / 9% HYDROSEAL G340H 47/53 ok non sèche 6 5% EMAG / 12% HYDROSEAL G3H 29/71 ok non sèche 7 7% EMAG / 10% HYDROSEAL G400H 41/59 ok non sèche (1) Le durcissement du mastic est évalué au toucher 24 heures après son application,
(2) Pour évaluer le ressuage, l'application du mastic est faite sur une fiche Bristol de type Exacompta 13308E. Après durcissement, la fiche est vérifiée de manière périodique afin de voir si l'huile migre vers la fiche Bristol.
(3) L'évaluation de l'humidité de la surface du mastic se fait visuellement. Table 2 groups together the results obtained for the various sealant formulations. <u> Table 2 </u> Example Plasticizer Plasticizer constituents ratio Hardening (1) Penetrant (2) Surface aspect (3) 1 comparative 17% HYDROSEAL G3H - OK yes (3d) Dried 2 comparative 17% HYDROSEAL G340H - OK yes, strong after 1 day (1d) wet 3 comparative 17% DIDP - OK no dried 4 8.5% FAME / 8.5% HYDROSEAL G340H 50/50 OK no Dried 5 8% FAME / 9% HYDROSEAL G340H 47/53 OK no dried 6 5% FAME / 12% HYDROSEAL G3H 29/71 OK no dried 7 7% FAME / 10% HYDROSEAL G400H 41/59 OK no dried (1) The hardening of the sealant is evaluated to the touch 24 hours after its application,
(2) To evaluate the bleeding, the application of the sealant is made on a Bristol sheet of the Exacompta 13308E type. After hardening, the plug is checked periodically to see if the oil is migrating to the Bristol plug.
(3) The evaluation of the moisture of the sealant surface is done visually.

Les résultats du tableau 2 montrent que les propriétés de la composition de mastic sont toutes aussi bonnes voire meilleures avec un plastifiant comprenant un fluide hydrocarboné en mélange avec un monoester d'acide gras. Le durcissement du mastic est satisfaisant, aucune humidité ni aucun ressuage n'est constaté.The results of Table 2 show that the properties of the mastic composition are all as good or even better with a plasticizer comprising a hydrocarbon fluid mixed with a fatty acid monoester. The curing of the sealant is satisfactory, no moisture or bleeding is observed.

Le tableau 3 regroupe les résultats obtenus pour d'autres formulations de mastics avec comme plastifiant la référence phtalates (exemple comparatif 1bis) et un plastifiant selon l'invention (exemple 8 selon l'invention).Table 3 groups together the results obtained for other sealant formulations with the reference phthalates as plasticizer (comparative example 1a) and a plasticizer according to the invention (example 8 according to the invention).

La formulation de l'exemple 1bis contient 17% d'un plastifiant qui est le Jayflex DIDP. La formulation de l'exemple 8 contient 17% d'un plastifiant qui est un mélange d'Hydroseal G340H et d'esters méthyliques d'acides gras (EMAG). Les pourcentages en masse d'Hydroseal G340H et des esters méthyliques d'acides gras (EMAG) sont respectivement de 8% et 9% par rapport à la masse de la formulation. Tableau 3 Exemple Ibis Exemple 8 Nature chimique / Propriétés DIDP composition (en % massique) EMAG/Hydroseal G340H composition (en % massique) Polymer MS 203H Polyéther à fonctions terminales de type silane / Polymère 15 15 Polymer MS 303H Polyéther à fonctions terminales de type silane / Polymère 10 10 Irganox 1076 anti-oxydant phénolique à empêchement stérique 0,2 0,2 Jayflex DIDP Di-isodecyl phthalate / Plastifiant 17 - Hydroseal G340H Hydroseal / Plastifiant - 8 EMAG Ester méthylique d'acide gras / Plastifiant - 9 Crayvallac SLX PA-wax / épaississant 5,5 5,5 Carbital 110S Chalk / charge 49,9 49,9 Dynasilan VTMO Vinyltrimethoxysilan/ agent séchant 0,8 0,8 Dynasilan AMMO 3-Aminopropylmethoxysilane / agent de réticulation 1,1 1,1 Tegokat 223 Dioctyltindiethanolate / Catalyseur 0,3 0,3 Tegokat 422 Dioctyltin-silane-blend / 0,2 0,2 Catalyseur TOTAL 100 100 Tableau 4 : Propriétés mécaniques Exemple Ibis Exemple 8 Caractéristiques DIDP EMAG/G340H Viscosité après 0 jour / 56 jours (en Pa.s) (Méthode interne) 6150 / 4800 4650 / 3450 Temps de formation de la peau (temps de lissage) après 0 jour / 56 jours (en min) (Méthode interne) 8 / 10 13 / 14 Dureté Shore A après 28 jours à température ambiante (DIN ISO 7619) 28 28 Résistance au cisaillement (application du mastic sur un substrat en bois) EN 281 après 3 jours (en N/mm2) (DIN EN 14293) 0,795 0,717 Résistance au cisaillement (application du mastic sur un substrat en bois) EN 281 après 3 jours (en mm) (DIN EN 14293) 2,0 0,9 Module d'élasticité à 100% (film de 2mm) 3 jours / 28 jours (en N/mm2) (DIN 53504, S2) 0,44 / 0,46 0,33 / 0,40 Résistance à la traction (film de 2 mm) 3 jours / 28 jours (en N/mm2) (DIN 53504, S2) 1,13 / 1,16 0,92 / 1,10 Allongement à la rupture à 3 jours / 28 jours (en %) (DIN 53504, S2) 1150 / 1150 1050 / 1000 Module d'élasticité à 1 00% (béton cycle A) à température ambiante (en N/mm2) (DIN 52455-1) 0,536 0,527 Module d'élasticité à 100% (aluminium cycle A) à température ambiante (en N/mm2) (DIN 52455-1) 0,518 0,494 Module d'élasticité à 1 00% (Béton cycle B) à température ambiante (en N/mm2) (DIN 52455-1) 0,461 0,461 Module d'élasticité à 100% (Béton cycle B) à -20°C (en N/mm2) (DIN 52455-1) 0,513 0,728 Module d'élasticité à 100% (Aluminium cycle B) à température ambiante (en N/mm2) (DIN 52455-1) 0,511 0,474 Reprise élastique à température ambiante (en %) (DIN EN ISO 7389-B) 64 78 The formulation of Example 1a contains 17% of a plasticizer which is Jayflex DIDP. The formulation of Example 8 contains 17% of a plasticizer which is a mixture of Hydroseal G340H and fatty acid methyl esters (FAME). The mass percentages of Hydroseal G340H and esters methyl fatty acids (FAME) are respectively 8% and 9% relative to the weight of the formulation. <u> Table 3 </u> Ibis example Example 8 Chemical nature / Properties DIDP composition (in% by mass) FAME / Hydroseal G340H composition (in% by mass) Polymer MS 203H Silane-type end-functional polyether / Polymer 15 15 Polymer MS 303H Silane-type end-functional polyether / Polymer 10 10 Irganox 1076 sterically hindered phenolic antioxidant 0.2 0.2 Jayflex DIDP Di-isodecyl phthalate / Plasticizer 17 - Hydroseal G340H Hydroseal / Plasticizer - 8 FAME Fatty Acid Methyl Ester / Plasticizer - 9 Crayvallac SLX PA-wax / thickener 5.5 5.5 Carbital 110S Chalk / charge 49.9 49.9 Dynasilan VTMO Vinyltrimethoxysilan / drying agent 0.8 0.8 Dynasilan AMMO 3-Aminopropylmethoxysilane / crosslinking agent 1.1 1.1 Tegokat 223 Dioctyltindiethanolate / Catalyst 0.3 0.3 Tegokat 422 Dioctyltin-silane-blend / 0.2 0.2 Catalyst TOTAL 100 100 Ibis example Example 8 Characteristics DIDP EMAG / G340H Viscosity after 0 day / 56 days (in Pa.s) (Internal method) 6150/4800 4650/3450 Skin formation time (smoothing time) after 0 day / 56 days (in min) (Internal method) 8/10 13/14 Shore A hardness after 28 days at room temperature (DIN ISO 7619) 28 28 Shear strength (application of mastic to a wooden substrate) EN 281 after 3 days (in N / mm 2 ) (DIN EN 14293) 0.795 0.717 Shear strength (application of mastic on a wooden substrate) EN 281 after 3 days (in mm) (DIN EN 14293) 2.0 0.9 Modulus of elasticity at 100% (2mm film) 3 days / 28 days (in N / mm 2 ) (DIN 53504, S2) 0.44 / 0.46 0.33 / 0.40 Tensile strength (2 mm film) 3 days / 28 days (in N / mm 2 ) (DIN 53504, S2) 1.13 / 1.16 0.92 / 1.10 Elongation at break at 3 days / 28 days (in%) (DIN 53504, S2) 1150/1150 1050/1000 Modulus of elasticity at 100% (concrete cycle A) at room temperature (in N / mm 2 ) (DIN 52455-1) 0.536 0.527 Modulus of elasticity at 100% (cycle A aluminum) at room temperature (in N / mm 2 ) (DIN 52455-1) 0.518 0.494 Modulus of elasticity at 100% (Concrete cycle B) at room temperature (in N / mm 2 ) (DIN 52455-1) 0.461 0.461 Modulus of elasticity at 100% (Concrete cycle B) at -20 ° C (in N / mm 2 ) (DIN 52455-1) 0.513 0.728 Modulus of elasticity at 100% (Aluminum cycle B) at room temperature (in N / mm 2 ) (DIN 52455-1) 0.511 0.474 Elastic recovery at room temperature (in%) (DIN EN ISO 7389-B) 64 78

On remarque que les propriétés mécaniques du mastic ST-PE contenant la composition EMAG/Hydroseal G340H en tant que plastifiant sont aussi bonnes voire meilleures que celles d'un mastic contenant du DIDP en tant que plastifiant.It is noted that the mechanical properties of the ST-PE mastic containing the composition EMAG / Hydroseal G340H as a plasticizer are as good or even better than those of a mastic containing DIDP as a plasticizer.

Claims (12)

  1. Composition comprising:
    a) at least one polymer chosen from the group consisting of a polyether comprising two terminal functions of silane type, a polyurethane comprising two terminal functions of silane type, a polyamide, or a mixture thereof;
    b) a plasticizer;
    c) at least one compound selected from the group consisting of a thickener, a filler, a crosslinking agent, a crosslinking catalyst and a tackifying resin, or a mixture thereof, said plasticizer comprising:
    i) at least one hydrocarbon cut or a cut resulting from the conversion of biomass, said cut being able to be produced from raw biological materials selected from the group consisting of vegetable oils, animal fats, fish oils and mixtures thereof, the raw biological materials undergoing a hydrodeoxygenation (HDO) step to decompose the structure of the constituent biological esters or triglycerides and to remove the compounds containing oxygen, phosphorus and sulfur while at the same time producing the hydrogenation olefinic bonds, followed by isomerization of the product thus obtained leading to branching of the hydrocarbon chain,
    ii) at least one fatty acid monoester, the fatty acids of the fatty acid monoester comprising from 6 to 24 carbon atoms;
    iii) less than 1% by weight of phthalates.
  2. Composition according to Claim 1, in which the plasticizer comprises at least one hydrocarbon cut.
  3. Composition according to claim 1 or 2, in which the hydrocarbon cut is a hydrotreated, hydrocracked or catalytically cracked hydrocarbon cut.
  4. Composition according to one of claims 1 to 3, in which the hydrocarbon cut is a dearomatized and / or desulphurized hydrocarbon cut.
  5. Composition according to one of claims 1 to 4, in which the hydrocarbon cut has a boiling point of between 230 and 400° C.
  6. Composition according to one of Claims 1 to 5, in which the hydrocarbon cut has a kinematic viscosity at 40° C of between 2 and 22 mm2/s according to standard ASTM D445.
  7. Composition according to one of Claims 1 to 6, in which the hydrocarbon cut has a pour point ranging from -50 to +10°C according to the ASTM D97 standard.
  8. Composition according to one of Claims 1 to 7, in which the hydrocarbon cut has a content of aromatic compounds measured by UV of less than 300 ppm, preferably less than 200 ppm and even more preferably less than 100 ppm.
  9. Composition according to one of claims 1 to 8, wherein the fatty acid monoester is a methyl ester of C 14-18 fatty acids.
  10. Composition according to one of claims 1 to 9, in which the mass ratio between the fatty acid monoester and the hydrocarbon cut or the cut resulting from the conversion of biomass is between 5:95 and 75:25, preferably between 10:90 and 60:40, more preferably between 20:80 and 45:55, even more preferably between 30:70 and 40:60.
  11. Composition according to one of claims 1 to 10, which is a mastic composition comprising:
    - at least one polymer chosen from the group consisting of a polyether comprising two terminal functions of silane type, a polyurethane comprising two terminal functions of silane type, or a mixture of these;
    - and at least one crosslinking agent.
  12. Composition according to one of claims 1 to 10, which is an adhesive composition comprising:
    - at least one polyamide;
    - an ethylene vinyl acetate copolymer;
    - a tackifying resin.
EP14761842.5A 2013-09-11 2014-09-09 Plasticiser for sealants and adhesives Active EP3044269B1 (en)

Priority Applications (1)

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PL14761842T PL3044269T3 (en) 2013-09-11 2014-09-09 Plasticiser for sealants and adhesives

Applications Claiming Priority (2)

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FR1358730A FR3010409B1 (en) 2013-09-11 2013-09-11 PLASTICIZER FOR MASTICS, PLASTISOLS AND ADHESIVES
PCT/EP2014/069160 WO2015036389A1 (en) 2013-09-11 2014-09-09 Plasticiser for sealants, plastisols and adhesives

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EP3044269A1 EP3044269A1 (en) 2016-07-20
EP3044269B1 true EP3044269B1 (en) 2021-10-27

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EP (1) EP3044269B1 (en)
JP (1) JP2016536431A (en)
KR (1) KR102252120B1 (en)
CN (1) CN105658737B (en)
AU (1) AU2014320493B2 (en)
BR (1) BR112016005224B1 (en)
CA (1) CA2923489A1 (en)
EA (1) EA031568B1 (en)
ES (1) ES2900629T3 (en)
FR (1) FR3010409B1 (en)
MX (1) MX2016003269A (en)
MY (1) MY183397A (en)
PL (1) PL3044269T3 (en)
SG (1) SG11201601849PA (en)
WO (1) WO2015036389A1 (en)
ZA (1) ZA201601547B (en)

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ES2900629T3 (en) 2022-03-17
EA201690572A1 (en) 2016-08-31
US20160222188A1 (en) 2016-08-04
KR102252120B1 (en) 2021-05-17
BR112016005224A2 (en) 2017-08-01
MX2016003269A (en) 2016-09-21
FR3010409A1 (en) 2015-03-13
SG11201601849PA (en) 2016-04-28
WO2015036389A1 (en) 2015-03-19
MY183397A (en) 2021-02-18
CN105658737A (en) 2016-06-08
FR3010409B1 (en) 2017-12-22
EP3044269A1 (en) 2016-07-20
JP2016536431A (en) 2016-11-24
US10351690B2 (en) 2019-07-16
BR112016005224B1 (en) 2022-02-01
ZA201601547B (en) 2017-05-31
AU2014320493B2 (en) 2018-04-19
CA2923489A1 (en) 2015-03-19
EA031568B1 (en) 2019-01-31
PL3044269T3 (en) 2022-02-21
CN105658737B (en) 2018-12-18
KR20160070752A (en) 2016-06-20

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